Stabilized liquid metal deactivator concentrate



STABILIZED LIQUID METAL DEACTIVATOR CONCENTRATE Frederick W. Rakowsky, Hammond, Ind., assignor to Standard Oil Company, Chicago, 111., a corporation of.

Indiana No Drawing. Application March 14,1958 Serial No. 721,350

11 Claims. or. 252-403) The present invention relates to liquid concentrates of certain metal deactivators, which'concentrates are resistant to crystallization at low temperatures. More particularly, the invention pertains to a metal deactivator concentrate, the principal ingredient of which is N,N'-

tdisalicylidene-l,2-propylenediamine, which is inhibited against low temperature crystallization.

It is known that the oxidative deterioration of organic substances, for example petroleum products, due to the United States-PatentQ 2,912,387 Patented'NQVQ 10., 19 5 9 2. atomswith an aliphatic polyamine having from-2'carbon atomsto about 10 carbon atoms and having atleast'one primary amino group. The aliphatic ketone and the aliphatic, amine can be used inweight ratios, of from about 1:1 to about 1:2 respectively. a r

The stabilized N,N'-disalicylidene polyamine solution can contain from about 2% to about 40% of the-aliphatic ketone-aliphatic polyamine. condensation product.

These condensation prodafter and inthe claims as an. N,N'-disalicylidene-polyamine.

Although such metal deactivators are used in amounts of from about 0.0002% to about 0.01%, based on the organic substance, eg, a petroleum product such as gasoline, the condensation products are usually marketed for use as an 8 0% solution in a hydrocarbon solvent,

preferably an aromatic hydrocarbon solvent such as benzene, toluene, xylenes and the like. It has been found that such solutions when stored or transported at winter ambient temperatures crystallization of the condensation product takes place. Such crystallization occurs even in more diluted concentrates, such as 60-65% of the condensation product in the solvent. When such crystallization takes place, the mixture must be heated to dissolve the crystals before the product can be used It is, therefore, an object of the present invention to provide a liquid concentrate of N,N'-disalicylidene-poly amines which will not crystallize out of solution at low temperatures. Another object of theinvention is to prepare concentrated solutions of an N,N'disalicylidenepolyamine mixture predominantly N,N';-disalieylidene- 1,2-propylenediamine metal deactivator in a normally liquid hydrocmbon solvent from which concentrated solutions themetal deactivator does not crystallize at low temperatures. Other objects and advantages of the invention will 'becomeapparentfrom the following description thereof.

In accordance with the .present invention, the foregoing objects, among others, can be attained by using in combination with an N,N'-disalicylidenepolyamine, as above defined, a condensation product of an aliphatic ketone having from 3 carbon atoms to about 10 carbon The ketone-polyamine stabilizcrican. be prepared before addition to the N,N'-salicylidenepolyamine, or it .canbe formed in situ by the addition of the aliphatic ketone and of the aliphatic polyamine; to the N,N'-salicylidenepolyamine. The ketone-polyamine condensation readily 7 takes places at temperatures in 70 F. to about 200 F.

Illustrative of the aliphatic ketones and of the aliphatic polyamines which can be used in accordance with the present invention are: v

the range of from about Ketones:

Acetone Methyl ethyl ketone Diethyl ketone Diacetone alcohol Methyl amyl ketone Methyl isopropyl ketone Methyl vinyl ketone Polyamines:

Ethylene diamine Propylene diamine 1,2-diamino butane 1,2-diamine pentane 1,3-diamino butane 1,4-diamino hexane 1,3,5-triamino pentane Hexamethylene diamine Hydroxyethyl ethylene diamine, Diethylene triamine Triethylene tetramine Tetraethylene pentamine While condensation products of the aliphatic ketones and aliphatic polyamines, illustrated by theabove specific compounds, are elfective for the. purpose. of the herein described invention, it is not tobe inferred that they are all equivalent in effectiveness, since under certain conditions some of such condensation products may be more eifective than others.

The aliphatic ketone-polyamine stabilizer can'be'used, if desired, in combination with normally'liquid solvents, such as alkanolsof from '1 to 4 carbon atoms, or 1137- drocarbon solvents, particularly a liquid'rnononuclear aromatic hydrocarbon such as. benzene, toluene and the xylenes. When used, such solvent can be employed in amounts of from 5% to about 20% a Y The effectiveness of the present invention in inhibiting the crystallization of an 'N,N'-disalicylidene-polyamine metal deactivator is demonstrated by the data in Table I.

These data were obtained by forming solutions of an N,N'-disalicylidene 1,2 propylenediamine with various amounts of aliphatic ketone-aliphatic polyamine condensation products, with and withoutv added solventsfand placing the resultant solutions .in a 0 F. cold chat. If no crystallization took place in 24 hours, the solutions were seeded with crystals of the N,N'-disalicylidene-1,2-

propylenediamine and returned to the cold chest. Solutions in, which no crystals formed after seeding were cycled between 40 F. and 0 F. for a week; solutions in which no crystals appeared during the test cycle werepolyamine having from 2--to about carbon atomsand considered stabilized against crystallization.

TABLE I at least one primary amino group, said acetone and said Efiect of various additives on inhibiting low temperature crystallization of N,N'-disalicylidene-1,2-propylenediamme (MD) Test No; MD, Keto'ne Wt. Polyainlne Wt. Solvent Wt. Effec- Wt; Percent P Percent Percent tlveness Percent 1' 80 5 Xylene..- g 1 95 None 2 80 2rv 80' 2O 2 80 I 10 2 80. 10 10 3 79" 7 7 Xylene..- 7 3 180' 10 10 None 3 90 5 5 n 3 85. 7.5 7.6 do '3 98 :1 1 do 3 80 10 10 d0 3 66.7 7:7 14.2 Xylene... 11.4 3 166.7, 7.7 14.2 Methanol. 11.4 3 66.7 7.7 14.2 do 11.4 3

I PDA-- Prcpylene diarnine; DETA=Dlethylene trlamine; orthydroxyethyl ethylene diamine) AEAEOL=2-(Z-aminoethylamint)ethanol,

Effectiveness rating: 1 Crystallization without seeding; 2= Crystallization after seeding; 3=No crystallization even after seeding.

The data in Table I show the effectiveness ofthe condensation products of an aliphatic ketone and an aliphatic polyamine in inhibiting low temperature crystallization of the herein'defined metal deactivator. Y

The .percentagesgiven herein and in theappended claims are weight percentages unless otherwise stated.

Having described my. invention by way' of specific examples, it is to be understood that the present invention is not limited thereto but embraces such variations and modifications as come within the spirit and scope ofthe' appended claims.

Iclaim: 7 M

'1. A liquid concentrate of 'an N,N -salicy1idene-polyamine which is resistant to low temperaturecrystallization, which concentrate consists essentially'of from about 60% to about 98% of an N,N'-salicylidene-polyamine, from 0% to about of an organic solvent selected carbon atoms and a normally liquidmononuclear aromatic hydrocarbon, and from about 2% to about 40% aliphatic polyamine being used in weight ratios of from about 1:1 to about 1:2 respectively, and said N,N sali cylidene-p'olyamine being the condensation product of twomols of salicylaldehyde with one mol. ofa polyamine selected from the group consisting of 1,2-propylenedi amine and mixtures of 1,2-propylene-diamine withr'up to 10 mol percent of diethylene-triamine; l a 6. A liquid concentrate as describedin claim 5 7. A liquid'concentrate as described in claimS in which the organic solvent is methanol.

8. A liquid concentrate as described in claim 5 in which the organic solvent is toluene.

' propylenediamine which is resistant to low temperature crystallization, which concentrate consists essentially of:

of a condensation product of an aliphaticketone having T from 3 to about 10 carbon atomsand an aliphatic polyamine having from 2 to aboutlO carbon'atoms and at *least one primary amino groupysaid aliphatic ketone and said aliphatic polyamine being used in weight ratios of salicylidene-polyamine being the condensation product of a two mols of salicylaldehyde' with one mol of a polyamine selected from 'the group consisting of 1;2-propylenediamine and mixtures of 1 ,2-pr0pylenediamine with up to 10 mol'percent of diethylene-triamine.

from about 1:1 to about 1:2 respectively, and said N,N-

2. Aliquid concentrate as described in claim 1 in which the aliphatic polyamine is propylenediamine.

3. A liquid concentrate as described in claim 1 in which the aliphatic polyamine is'diethylenetriamine.

4. A liquid concentrate as described in claim 1 in which V 1 the aliphatic polyamineis hydroxyethyl ethylene diamine. j

5. A-liquid concentrate of 'an N,N-salicylidene-poly- 1 V amine which-is resistant to lowtemperature crystallization, which concentrate consists essentially of from about -propylenediamine,- and from about.2% to about 20% of a condensation product of acetone and diethylerietti- .amine,'saidacetone and said diethylenetriamine ib'eing used'in weightratios of 1:1.

10. A liquidconcentrate as described which the organic solvent is Xylene.

11. A liquid concentrate of an N,N'-salicylidene-polyamine which is resistant to low temperature crystallization, which concentrate consists essentially of from about to about 98% of an N,N'-salicylidene-polyamine, from 0% to about 20% of an organic solventselected from the group consisting of an alkanol of from 1 to 4 carbon atoms and a normally liquid mononuclear aro- -matic hydrocarbon, and from about 2% to about 40% a of a condensation product of acetone and propylenediamine, said acetone and said, propylenediamine being used 'in weight ratios of about 1:1, and said N,N-'s alicyli- .dene-polyamine being the condensation product of two 'mols of salicylaldehyde with one mole of a polyarhine selected'from the group consisting of 1,2-propylenediamine and. mixtures of 1,2-propylene-diamine with up to l0.mol percent of diethylene-triamine.

References Cited in the file'of this patent ,UNITED STATES PATENTS 7 V 9. A liquid concentrate of an N,N-sali :ylidene- 1,2-

in claim 9 in 

1. A LIQUID CONCENTRATE OF AN N,N''-SALICYLIDENE-POLYAMINE WHICH IS RESISTANT TO LOW TEMPERATURE CRYSTALLIZATION, WHICH CONCENTRATE CONSISTS ESSENTIALLY OF FROM ABOUT 60% TO ABOUT 98% OF AN N,N''-SALICYLIDENE-POLYAMINE, FROM 0% TO ABOUT 20% OF AN ORGANIC SOLVENT SELECTED FROM THE GROUP CONSISTING OF AN ALKANOL OF FROM 1 TO 4 CARBON ATOMS AND A NORMALLY LIQUID MONONUCLEAR AROMATIC HYDROCARBON, AND FROM ABOUT 2% TO ABOUT 40% OF A CONDENSATION PRODUCT OF AN ALIPHATIC KETONE HAVING FROM 3 TO ABOUT 10 CARBON ATOMS AND AN ALIPHATIC POLYAMINE HAVING FROM 2 TO ABOUT 10 CARBON ATOMS AND AT LEAST ONE PRIMARY AMINO GROUP, SAID SLIPHATIC KETONE AND SAID ALIPHATIC POLYMINE BEING USED IN WEIGHT RATIOS OF FROM ABOUT 1:1 TO ABOUT 1:2 RESPECTIVELY, AND SAID N,N'' SALICYLIDENE-POLYAMINE BEING THE CONDENSATION PRODUCT OF TWO MOLS OF SALICYLALDEHYDE WITH ONE MOL OF A POLYAMINE SELECTED FROM THE GROUP CONSISTING OF 1,2-PROPYLENEDIAMINE AND MIXTURES OF 1,2-PROPYLENEDIAMINE WITH UP TO 10 MOL PERCENT OF DIETHYLENE-TRIAMINE. 